EP2379327B1 - Élément de construction de forme plate fait d'un matériau composite - Google Patents

Élément de construction de forme plate fait d'un matériau composite Download PDF

Info

Publication number
EP2379327B1
EP2379327B1 EP09763973.6A EP09763973A EP2379327B1 EP 2379327 B1 EP2379327 B1 EP 2379327B1 EP 09763973 A EP09763973 A EP 09763973A EP 2379327 B1 EP2379327 B1 EP 2379327B1
Authority
EP
European Patent Office
Prior art keywords
sheet
monomers
layer
weight
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP09763973.6A
Other languages
German (de)
English (en)
Other versions
EP2379327A1 (fr
Inventor
Marco Schmidt
Marco Balbo Block
Volker Schmidt
Annerose Heimes-Scheller
Lothar Jandel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Akzo Nobel Coatings International BV
Original Assignee
BASF Coatings GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Priority to PL09763973T priority Critical patent/PL2379327T3/pl
Priority to EP09763973.6A priority patent/EP2379327B1/fr
Publication of EP2379327A1 publication Critical patent/EP2379327A1/fr
Application granted granted Critical
Publication of EP2379327B1 publication Critical patent/EP2379327B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/046—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0004—Use of compounding ingredients, the chemical constitution of which is unknown, broadly defined, or irrelevant
    • C08J9/0009—Phase change materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
    • E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
    • E04C2/26—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups
    • E04C2/284—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups at least one of the materials being insulating
    • E04C2/292—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups at least one of the materials being insulating composed of insulating material and sheet metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0278—Polyurethane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/72—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49616—Structural member making
    • Y10T29/49623—Static structure, e.g., a building component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/24992—Density or compression of components
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249987—With nonvoid component of specified composition
    • Y10T428/249988—Of about the same composition as, and adjacent to, the void-containing component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249987—With nonvoid component of specified composition
    • Y10T428/24999—Inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249987—With nonvoid component of specified composition
    • Y10T428/249991—Synthetic resin or natural rubbers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2984—Microcapsule with fluid core [includes liposome]
    • Y10T428/2985—Solid-walled microcapsule from synthetic polymer
    • Y10T428/2987—Addition polymer from unsaturated monomers only
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2989—Microcapsule with solid core [includes liposome]

Definitions

  • the present application relates to a sheet-like component made of composite material comprising two metallic cover layers and a rigid polyurethane foam layer.
  • Sheet-like construction elements comprising two metallic cover layers and a rigid polyurethane foam layer, so-called sandwich elements, are used both as components in residential construction and in industrial construction for hall roofs and facades, as structural elements in cold store construction, in sectional doors, in office containers or in caravan construction. Due to their very good insulation properties, they are widely used there. Their low mass, however, causes the buildings can hardly buffer temperature peaks. Due to internal and external temperature loads, such buildings heat up very quickly inside. This negative characteristic is summarized under the term "barrack climate”.
  • the mass of a building stores the incoming heat during the day and thus ideally keeps the internal temperature constant. In the cooler night, the stored heat is released back to the outside air. In order to achieve a pleasant indoor climate even in the summer without active air conditioning, so the thermal mass of the building is essential. However, such a large thermal mass is missing buildings with sandwich elements.
  • latent heat storage materials also referred to as phase change materials (PCMs for short) - have been investigated as a new material combination in building materials. Their function is based on the transformation enthalpy occurring during the solid / liquid phase transition, which means an energy absorption or energy release to the environment at a constant temperature. They can thus be used for temperature maintenance in a defined temperature range. Since the latent heat storage materials are also liquid depending on the temperature, they can not be processed directly with building materials, because emissions to the room air or the separation of the building material would be to be feared.
  • PCMs phase change materials
  • the EP-A-1 703 033 teaches components for interior fitting with two metal cover layers, wherein the intermediate layer contains a latent heat storage material.
  • the WO 2006/021306 teaches a composite material with a metal topcoat, a gypsum board, and a rigid polyurethane foam layer connecting these two panels.
  • the gypsum board contains microcapsules with a capsule core of latent heat storage material.
  • building elements with plasterboard have one on 2 to 3 meters limited span, which limits their applications. Thus, for example, the use in larger areas spanning roof structures is not possible.
  • the object of the present invention was to provide components which have improved mechanical stability, in particular an improved span.
  • Another object was to find an improved manufacturing method for such components, which makes it possible to produce them endlessly.
  • Object of the present invention was to improve sheet-like components made of a composite material with two metal cover layers such that the buildings made from them have a better climate.
  • a sheet-like component made of composite material comprising two metallic cover layers, a polyurethane foam layer and a polyurethane compact layer containing microcapsules with a capsule core of latent heat storage material.
  • the polyurethane compact layer contains microcapsules with a capsule core of latent heat storage material.
  • sheet-like component is to be understood to mean a structure whose thickness is small compared to both its length and its width. Its thickness is preferably ⁇ 1/5 of its length as well as its width.
  • the sheet-like components may have a topology, which is generated for example by shaping process.
  • the metallic cover layer A' is usually outdoors. Furthermore, indoor applications are conceivable as ceiling panels, wall panels and room-in-room systems. For applications such as room-in-room systems or internal partitions, sheet-like construction elements having the structure A-B-C-B-A are preferred.
  • the two metallic cover layers can be different. One then distinguishes the boundary to the interior of the room (A) and the outer covering layer (A '). The two layers do not have to agree either in their form or in their material. On the other hand, surface-shaped components with the construction A-B-C-B-A preferably have the same metallic cover layers.
  • cover layers flexible or rigid, preferably rigid cover layers can be used.
  • the topcoat does not necessarily have to be profiled, but can also be used in a smooth form or as a stamped, contoured or formed sheet (e.g., pan optics).
  • the metallic cover layer may be present in the metallic state or in the coated state.
  • Preferred metals are aluminum, steel, galvanized or aluminized steel, copper, zinc, other metal strips or metal sheets. Preference should be given to aluminum foils, aluminum, copper or steel sheets, particularly preferably steel sheets.
  • the metallic cover layers can be pretreated, for example by corona, arc, plasma or other conventional methods.
  • the metallic cover layer, preferably the outer metallic cover layer (A '), can be modified with the usual materials used for such components in order to increase the weather resistance.
  • the metallic cover layers are also provided with organic coatings. These organic layers may have a thickness of 0.5 ⁇ m to 500 ⁇ m.
  • An important coating process is coil coating, also known as coil coating.
  • the metal strips very often galvanized steel and aluminum strips up to a width of 2070 mm, coated with a paint or plastic film, rewound and then processed by the processor, for example, to sandwich panels.
  • the coil coating process is known to the person skilled in the art and is described, for example, in Kittel - Textbook of paints and Coatings, Volume 6 "Application of paints and other coatings", 2nd edition, S. Hirzel Verlag, Stuttgart, 2008 described.
  • the organic coatings applied to the metal strip can be applied in a single-layered or multi-layered manner with up to 6 layers on the top side. On the underside, which comes into contact during further processing with the polyurethane foam layer, usually one or two organic layers are applied.
  • the organic coatings may be composed of epoxy, polyester, polyurethane, acrylate, polyvinyl chloride (with plasticizers or esters) and polyvinylidene fluoride based resins. Typical crosslinkers are based on amino resins and / or isocyanate.
  • the organic coatings also have components such as pigments, catalysts, additives.
  • polyurethane compact layer is meant a polymer layer having a density of from 400 to 1200, preferably from 500 to 1000, particularly preferably from 600 to 950 kg / m 3 .
  • the reaction ratio is preferably selected such that in the reaction mixture the ratio of the number of isocyanate groups to the number of isocyanate-reactive hydrogen atoms is 0.8 to 1.8 to 1, preferably 1 to 1.6 to 1.
  • Suitable organic di- and polyisocyanates a) are aliphatic, cycloaliphatic and preferably aromatic polyfunctional isocyanates. Specific examples include 2,4- and 2,6-toluene diisocyanate (TDI) and the corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate (MDI) and the corresponding mixtures of isomers, mixtures of 4,4'- and 2,4'-diphenylmethane diisocyanates, polyphenyl polymethylene polyisocyanates, mixtures of 4,4'-, 2,4'- and 2,2'- diphenylmethane diisocyanates and polyphenyl polymethylene - Polyisocyanates (crude MDI) and mixtures of crude MDI and toluene diisocyanates.
  • the organic di- and polyisocyanates can be used individually or in the form of mixtures.
  • modified polyfunctional isocyanates ie products obtained by chemical reaction of organic di- and / or polyisocyanates are used. Examples include uretdione, carbamate, carbodiimide, allophanate, isocyanurate and / or urethane groups-containing di- and / or polyisocyanates.
  • the modified organic diisocyanates and polyisocyanates may optionally be mixed with one another or with unmodified organic diisocyanates and polyisocyanates, such as 2,4'-, 4,4'-diphenylmethane diisocyanate, crude MDI, 2,4- and / or 2,6- Toluylene diisocyanate are mixed.
  • reaction products of polyfunctional isocyanates with polyhydric polyols so-called prepolymers, and mixtures thereof with other diisocyanates and polyisocyanates.
  • Suitable compounds having at least two isocyanate-reactive hydrogen atoms b) are generally those which carry at least two reactive groups selected from OH, SH, NH, NH 2 groups and CH-acidic groups in the molecule, in particular polyetherpolyols and polyester polyols.
  • the polyester polyols are usually obtained by condensation of polyfunctional alcohols, preferably diols, having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, such as ethylene glycol, diethylene glycol, butanediol, trimethylolpropane, glycerol, pentaerythritol, with polyfunctional carboxylic acids having 2 to 12 carbon atoms, for example succinic acid, Glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid and preferably phthalic acid, isophthalic acid, terephthalic acid, the isomers of naphthalenedicarboxylic acids or the anhydrides of the acids.
  • polyfunctional alcohols preferably diols, having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, such as ethylene glycol, diethylene glycol, butanediol,
  • the hydrophobic substances are water-insoluble substances which contain a non-polar organic radical and have at least one reactive group selected from hydroxyl, carboxylic acid, carboxylic acid esters or mixtures thereof.
  • the equivalent weight of the hydrophobic materials is preferably between 130 and 1000 g / mol.
  • fatty acids such as stearic acid, oleic acid, palmitic acid, lauric acid or linoleic acid, as well as fats and oils such as castor oil, corn oil, sunflower oil, soybean oil, coconut oil, olive oil or tall oil.
  • the proportion of hydrophobic substances in the total monomer content of the polyester polyol is preferably 1-30 mol%, particularly preferably 4-15 mol%.
  • the polyester polyols used usually have a functionality of 1.5-4 and an OH number of 50-400, preferably 150-300 mg KOH / g.
  • the polyether polyols are prepared by known processes, for example by anionic polymerization of alkylene oxides with addition of at least one starting molecule in the presence of catalysts, for example alkali metal hydroxides.
  • alkylene oxides used are usually ethylene oxide and / or propylene oxide, preferably pure 1,2-propylene oxide.
  • starting molecules having at least 2, preferably 2 to 8 hydroxyl groups in the molecule are preferably propylene glycol, dipropylene glycol, trimethylolpropane, glycerol, pentaerythritol, sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resoles such as oligomeric condensation products of phenol and formaldehyde and Mannich - Condensates of phenols, formaldehyde and dialkanolamines and melamine used.
  • starting molecules having at least two primary amino groups in the molecule are preferably aromatic di- and / or polyamines, for example phenylenediamines, 2,3-, 2,4-, 3,4- and 2,6-toluenediamine and 4,4'-, 2 , 4'- and 2,2'-diaminodiphenylmethane and aliphatic di- and polyamines, such as ethylenediamine used.
  • aromatic di- and / or polyamines for example phenylenediamines, 2,3-, 2,4-, 3,4- and 2,6-toluenediamine and 4,4'-, 2 , 4'- and 2,2'-diaminodiphenylmethane and aliphatic di- and polyamines, such as ethylenediamine used.
  • the polyether polyols have a functionality of 2 to 4, preferably 2 to 3, and hydroxyl numbers of preferably 30 mg KOH / g to 800 mg KOH / g and in particular 150 mg KOH / g to 570 mg KOH / g.
  • the compounds having at least two isocyanate-reactive hydrogen atoms b) also include the optionally used chain extenders and crosslinkers.
  • chain extenders and crosslinking agents are preferably used alkanolamines, diols and / or triols, especially diols and / or triols having molecular weights less than 400, preferably 60 to 300.
  • Chain extenders, crosslinking agents or mixtures thereof are expediently used in an amount of 1 to 30% by weight, preferably 2 to 10% by weight, based on component b), preferably the polyol component.
  • the preparation of the polyurethane compact layer is usually carried out in the presence of catalysts and, if necessary, further auxiliaries and / or additives which are generally known in polyurethane chemistry and in which DE-A-101 24 333 described, to which express reference is made.
  • auxiliaries and / or additives are the substances known per se for this purpose, for example surface-active substances, fillers, pigments, dyes, flameproofing agents, hydrolysis protection agents, antistatic agents, fungistatic and bacteriostatic agents.
  • catalysts it is possible to use all compounds which accelerate the isocyanate-water reaction or the isocyanate-polyol reaction. These include amine-based catalysts and catalysts based on organic metal compounds.
  • organic tin compounds such as tin (II) salts of organic carboxylic acids, such as tin (II) acetate, tin (II) octoate, tin (II) ethyl hexoate and tin (II) laurate and the dialkyltin (IV) salts of organic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate, and also bismuth carboxylates such as bismuth (III) neodecanoate, bismuth-2 ethylhexanoate and bismuth octanoate or alkali metal salts of carboxylic acids such as potassium acetate or potassium formate.
  • organic tin compounds such as tin (II) salts of organic carboxylic acids, such as tin (II) acetate, t
  • the catalyst used is preferably a mixture containing at least one tertiary amine.
  • These tertiary amines are usually compounds which may also carry isocyanate-reactive groups, such as OH, NH or NH 2 groups.
  • Some of the most commonly used catalysts are bis (2-dimethylaminoethyl) ether, N, N, N, N-pentamethyldiethylenetriamine, N, N, N-triethylaminoethoxyethanol, dimethylcyclohexylamine, dimethylbenzylamine, triethylamine, triethylenediamine, pentamethyldipropylenetriamine, dimethylethanolamine , N-methylimidazole, N-ethylimidazole, tetramethylhexamethylenediamine, tris (dimethylaminopropyl) hexahydrotriazine, dimethylaminopropylamine, N-ethylmorpholine, diazabicy
  • Suitable flame retardants are, for example, brominated ethers (Ixol B 251), brominated alcohols, such as dibromoneopentyl alcohol, tribromoneopentyl alcohol and PHT-4-diol.
  • bromine-free flame retardants are used, such as chlorinated phosphates, e.g. Tris (2-chloroethyl) phosphate, tris (2-chloroisopropyl) phosphate (TCPP), tris (1,3-dichloroisopropyl) phosphate, and tetrakis (2-chloroethyl) ethylenediphosphate, or mixtures thereof.
  • inorganic flameproofing agents such as red phosphorus, red phosphorus-containing finishes, expandable graphite, alumina hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate or cyanuric acid derivatives such as melamine, or mixtures of at least two flame retardants such as ammonium polyphosphates and melamine and optionally starch.
  • DEEP Diethyl ethane phosphonate
  • TEP triethyl phosphate
  • DMPP dimethyl propyl phosphonate
  • DPK diphenyl cresyl phosphate
  • the flame retardants are used in the context of the present invention preferably in an amount of 0 to 25% based on the total weight of the components of the polyurethane compact system.
  • the diisocyanates and polyisocyanates and the compounds containing isocyanate-reactive hydrogen atoms are reacted with one another in amounts such that the isocyanate index is in a range between 90 and 700, preferably in the range from 100 to 140.
  • the polyurethane compact layer is produced without the addition of blowing agents.
  • the polyols used may still contain residual water, which acts as a blowing agent.
  • the proportion of water can be reduced by "drying" the polyols by water-absorbing additives such as molecular sieve (physically active additives) or oxazolidines (chemically active additives).
  • an anti-foaming agent or water-absorbing additives is additionally added to the reactive polyurethane compact system.
  • microcapsules The microcapsules
  • the microcapsules according to the invention contained in the polyurethane compact layer comprise a capsule core of latent heat storage material and a capsule wall of polymer.
  • the capsule core consists predominantly, to more than 95 wt .-%, of latent heat storage material.
  • the capsule core can be both solid and liquid, depending on the temperature.
  • a protective colloid is generally incorporated into the capsule wall and is thus likewise part of the capsule wall.
  • the surface of the polymer in particular has the protective colloid.
  • the average particle size of the capsules (Z means by means of light scattering) is 0.5 to 50 ⁇ m, preferably 0.5 to 30 ⁇ m.
  • the weight ratio of capsule core to capsule wall is generally from 50:50 to 95: 5.
  • Preferred is a core / wall ratio of 70:30 to 93: 7.
  • latent heat storage materials are substances which have a phase transition in the temperature range in which heat transfer is to be carried out, and are therefore often referred to in the literature as PCM (Phase Change Material).
  • PCM Phase Change Material
  • it is an organic lipophilic substance having its solid / liquid phase transition in the temperature range of -20 to 120 ° C.
  • Examples include:
  • mixtures of these substances are suitable, as long as it does not come to a melting point lowering outside the desired range, or the heat of fusion of the mixture is too low for a meaningful application.
  • n-alkanes for example, the use of pure n-alkanes, n-alkanes with a purity of greater than 80% or of alkane mixtures, as obtained as a technical distillate and are commercially available as such.
  • soluble compounds may be added to the lipophilic substances so as to prevent the crystallization delay which sometimes occurs with the non-polar substances.
  • Suitable compounds are the fatty acids mentioned above as lipophilic substances, fatty alcohols, fatty amides and aliphatic hydrocarbon compounds. They are added in amounts of from 0.1 to 10% by weight, based on the capsule core.
  • the latent heat storage materials are - depending on the temperature range in which the heat storage are desired - selected.
  • Preferred latent heat storage materials are aliphatic hydrocarbons, particularly preferably those listed above by way of example.
  • aliphatic hydrocarbons having 14 to 20 carbon atoms and mixtures thereof are preferred.
  • the materials known for the microcapsules for copying papers can be used as the polymer for the capsule wall. So it is possible, for example, the latent heat storage materials according to in the GB-A 870476 . US 2,800,457 . US 3,041,289 to encapsulate in gelatin with other polymers.
  • thermosetting wall materials are thermosetting polymers. Under thermosetting wall materials are to be understood that do not soften due to the high degree of crosslinking, but decompose at high temperatures. Suitable thermosetting wall materials are, for example, highly crosslinked formaldehyde resins, highly crosslinked polyureas and highly crosslinked polyurethanes, as well as highly crosslinked methacrylic acid ester polymers and uncrosslinked methacrylic acid ester polymers.
  • formaldehyde resins are urea-formaldehyde resins, urea-resorcinol-formaldehyde resins, urea-melamine resins and melamine-formaldehyde resins.
  • C 1 -C 4 alkyl, in particular methyl ether of these formaldehyde resins and the mixtures with these formaldehyde resins are preferred.
  • melamine-formaldehyde resins and / or their methyl ethers are preferred.
  • the resins are used as prepolymers.
  • the prepolymer is still soluble in the aqueous phase and migrates in the course of the polycondensation at the interface and surrounds the oil droplets.
  • Methods for microencapsulation with formaldehyde resins are well known and are described, for example, in US Pat EP-A-562,344 and EP-A-974 394 described.
  • Capsule walls of polyureas and polyurethanes are also known from the copying papers.
  • the capsule walls are formed by reaction of NH 2 groups or OH-containing reactants with di- and / or polyisocyanates.
  • Suitable isocyanates are, for example, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate and 2,4- and 2,6-toluene diisocyanate.
  • polyisocyanates such as biuret derivatives, polyuretonimines and isocyanurates.
  • Suitable reactants are: hydrazine, guanidine and its salts, hydroxylamine, di- and polyamines and amino alcohols.
  • Such interfacial polyaddition processes are known, for example, from US 4,021,595 .
  • EP-A 0 392 876 and EP-A 0 535 384 known.
  • Preference is given to microcapsules whose capsule wall is an uncrosslinked or crosslinked methacrylic ester polymer.
  • the polymers of the capsule wall generally contain at least 30 wt .-%, preferably at least 40 wt .-%, in a particularly preferred form at least 50 wt .-%, in particular at least 60 wt .-%, most preferably at least 70 wt.
  • the polymers of the capsule wall preferably contain at least 10% by weight, preferably at least 15% by weight, preferably at least 20% by weight and generally at most 70% by weight, preferably at most 60% by weight and in particular more preferably Form at most 50 wt .-% of one or more bi- or polyfunctional monomers which are insoluble or sparingly soluble in water (monomers II) polymerized, based on the total weight of the monomers.
  • the polymers may contain up to 40% by weight, preferably up to 30% by weight, in particular up to 20% by weight, of other monomers III in copolymerized form.
  • the capsule wall is composed only of monomers of groups I and II.
  • the capsule wall of the microcapsules is made up of From 30 to 100% by weight one or more monomers (monomers I) from the group comprising C 1 -C 24 -alkyl esters of acrylic and / or methacrylic acid, acrylic acid, methacrylic acid and maleic acid, 0 to 70% by weight one or more bi- or polyfunctional monomers (monomers II) which is insoluble or sparingly soluble in water and 0 to 40% by weight one or more other monomers (monomers III), in each case based on the total weight of the monomers.
  • Suitable monomers I are C 1 -C 24 -alkyl esters of acrylic and / or methacrylic acid and the unsaturated C 3 - and C 4 -carboxylic acids, such as acrylic acid, methacrylic acid and maleic acid.
  • Suitable monomers I are isopropyl, isobutyl, sec-butyl and tert-butyl acrylate and the corresponding methacrylates, and particularly preferably methyl, ethyl, n-propyl and n-butyl acrylate and the corresponding methacrylates , Generally, the methacrylates and methacrylic acid are preferred.
  • the microcapsule walls contain from 25% by weight to 75% by weight of maleic acid, methacrylic acid and / or acrylic acid, in particular methacrylic acid, based on the total amount of monomers I, in copolymerized form.
  • Suitable monomers II are bi- or polyfunctional monomers which are insoluble or sparingly soluble in water but have good to limited solubility in the lipophilic substance. Low solubility is to be understood as meaning a solubility of less than 60 g / l at 20 ° C.
  • bi- or polyfunctional monomers is meant compounds having at least two non-conjugated ethylenic double bonds.
  • divinyl and polyvinyl monomers come into consideration. They cause a crosslinking of the capsule wall during the polymerization.
  • One or more divinyl monomers and one or more polyvinyl monomers and divinyl monomers may be copolymerized in admixture with polyvinyl monomers.
  • monomer II used is a mixture of divinyl and polyvinyl monomers, the proportion of polyvinyl monomers being from 2 to 90% by weight, based on the sum of divinyl and polyvinyl monomers.
  • the proportion of polyvinyl monomers is preferably from 5 to 80% by weight, preferably from 10 to 60% by weight, based on the sum of divinyl and polyvinyl monomers.
  • Suitable divinyl monomers are divinylbenzene and divinylcyclohexane.
  • Preferred divinyl monomers are the diesters of diols with acrylic acid or methacrylic acid, furthermore the diallyl and divinyl ethers of these diols. Examples which may be mentioned are ethanediol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, methallyl methacrylamide, allyl acrylate and allyl methacrylate. Particularly preferred are propanediol, butanediol, pentanediol and hexanediol diacrylate and the corresponding methacrylates.
  • Preferred polyvinyl monomers are the polyesters of polyols with acrylic acid and / or methacrylic acid, furthermore the polyallyl and polyvinyl ethers of these polyols, trivinylbenzene and trivinylcyclohexane. Particularly preferred are trimethylolpropane triacrylate and methacrylate, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, pentaerythritol triacrylate and pentaerythritol tetraacrylate and their technical mixtures.
  • divinyl and polyvinyl monomers such as butanediol diacrylate and pentaerythritol tetraacrylate, hexanediol diacrylate and pentaerythritol tetraacrylate, butanediol diacrylate and trimethylolpropane triacrylate, and also hexanediol diacrylate and trimethylolpropane triacrylate.
  • Suitable monomers III are other monomers which are different from the monomers I and II, such as vinyl acetate, vinyl propionate, vinylpyridine and styrene or ⁇ -methylstyrene. Particularly preferred are itaconic acid, vinylphosphonic acid, maleic anhydride, 2-hydroxyethyl acrylate and methacrylate, acrylamido-2-methylpropanesulfonic acid, methacrylonitrile, acrylonitrile, methacrylamide, N-vinylpyrrolidone, N-methylolacrylamide, N-methylolmethacrylamide, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.
  • the production process of the microcapsules is a so-called in situ polymerization.
  • the principle of microcapsule formation is based on the preparation of a stable oil-in-water emulsion from the monomers, a radical initiator, the protective colloid and the lipophilic substance to be encapsulated. Subsequently, the polymerization of the monomers is initiated by heating and optionally controlled by further increase in temperature, wherein the resulting polymers form the capsule wall, which encloses the lipophilic substance.
  • This general principle is used for example in the DE-A-101 39 171 whose contents are expressly referred to.
  • the starting emulsion is stabilized using a protective colloid.
  • Organic protective colloids are preferably water-soluble polymers which reduce the surface tension of the water from 73 mN / m to a maximum of 45 to 70 mN / m and thus ensure the formation of closed capsule walls and microcapsules with preferred particle sizes in the range of 0.5 to 50 .mu.m, preferably 0 , 5 to 30 microns in particular 0.5 to 10 microns, form.
  • Organic neutral protective colloids are, for example, cellulose derivatives such as hydroxyethylcellulose, methylhydroxyethylcellulose, methylcellulose and carboxymethylcellulose, polyvinylpyrrolidone, copolymers of vinylpyrrolidone, gelatin, gum arabic, xanthan, casein, polyethylene glycols, polyvinyl alcohol and partially hydrolyzed polyvinyl acetates and also methylhydroxypropylcellulose.
  • Preferred organic neutral protective colloids are polyvinyl alcohol and partially hydrolyzed polyvinyl acetates and methylhydroxypropyl cellulose. These protective colloids are in the WO 2008/046839 whose contents are expressly referred to.
  • Organic anionic protective colloids are sodium alginate, polymethacrylic acid and its copolymers, polyacrylic acid and its copolymers, the copolymers of Sulfoethyl acrylate and methacrylate, sulfopropyl acrylate and methacrylate, N- (sulfoethyl) -maleimide, 2-acrylamido-2-alkylsulfonic acids, styrenesulfonic acid and vinylsulfonic acid.
  • Preferred organic anionic protective colloids are naphthalenesulfonic acid and naphthalenesulfonic acid-formaldehyde condensates and especially polyacrylic acids and phenolsulfonic acid-formaldehyde condensates.
  • a Pickering system can consist of the solid particles alone or in addition of auxiliaries which improve the dispersibility of the particles in water or the wettability of the particles by the lipophilic phase.
  • the inorganic solid particles may be metal salts, such as salts, oxides and hydroxides of calcium, magnesium, iron, zinc, nickel, titanium, aluminum, silicon, barium and manganese.
  • metal salts such as salts, oxides and hydroxides of calcium, magnesium, iron, zinc, nickel, titanium, aluminum, silicon, barium and manganese.
  • These include magnesium hydroxide, magnesium carbonate, magnesium oxide, calcium oxalate, calcium carbonate, barium carbonate, barium sulfate, titanium dioxide, aluminum oxide, aluminum hydroxide and zinc sulfide.
  • Silicates, bentonite, hydroxyapatite and hydrotalcites are also mentioned. Particularly preferred are highly disperse silicas, magnesium pyrophosphate and tricalcium phosphate.
  • the Pickering systems can be added to the water phase first as well as added to the stirred emulsion of oil-in-water. Some fine, solid particles are made by precipitation, as in the EP-A-1 029 018 , as well as the EP-A-1 321 182 described.
  • the highly dispersed silicas can be dispersed as fine, solid particles in water. But it is also possible to use so-called colloidal dispersions of silica in water. Such colloidal dispersions are alkaline, aqueous mixtures of silica. In the alkaline pH range, the particles are swollen and stable in water. For use of these dispersions as Pickering system, it is advantageous if the pH of the oil-in-water emulsion is adjusted to pH 2 to 7 with an acid.
  • the protective colloids are used in amounts of from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight, based on the water phase.
  • Organic protective colloids are preferred used in amounts of 0.1 to 10 wt .-%, based on the water phase of the emulsion.
  • inorganic protective colloids and their mixtures with organic protective colloids are preferred.
  • organic neutral protective colloids are preferred.
  • Protective colloids carrying OH groups are preferred, such as polyvinyl alcohols and partially hydrolyzed polyvinyl acetates.
  • surfactants preferably nonionic surfactants.
  • Suitable surfactants can be found in the "Handbook of Industrial Surfactants", the contents of which are expressly incorporated by reference.
  • the surfactants can be used in an amount of 0.01 to 10 wt .-% based on the water phase of the emulsion.
  • the rigid foams used for composite elements made of rigid polyurethane foam have long been known and widely described in the literature. If a reactive foam system is mentioned below, this is understood to mean the mixture of the starting components.
  • rigid polyurethane foam is meant a polymer layer having an average density of from 20 to 150, preferably from 25 to 100, particularly preferably from 30 to 70, kg / m 3 .
  • rigid polyurethane foam is preferably understood to mean a foam according to DIN 7726, i. the foam has a compression stress at 10% compression or compressive strength according to DIN 53 421 / DIN EN ISO 604 of greater than or equal to 80 kPa, preferably greater than or equal to 150 kPa. Furthermore, the rigid polyurethane foam according to DIN ISO 4590 has a closed cell density of greater than 85%, preferably greater than 90%.
  • the isocyanate index is understood as meaning the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups multiplied by 100.
  • Isocyanate-reactive groups are understood to mean all isocyanate-reactive groups, including chemical blowing agents, contained in the reaction mixture, but not the isocyanate group itself.
  • the isocyanates and the compounds containing isocyanate-reactive hydrogen atoms are reacted with each other in such amounts that the isocyanate index is in a range from 100 to 700, preferably from 115 to 180. In a further preferred embodiment, an isocyanate index of from 180 to 700, in particular from 200 to 500, is used. This is referred to as so-called polyisocyanurate-modified polyurethane foams or PolyisocyanuratMinen.
  • They are usually prepared by reacting organic di- and / or polyisocyanates a) with compounds having at least two isocyanate-reactive hydrogen atoms b), preferably polyols.
  • Suitable organic diisocyanates and polyisocyanates a) are the abovementioned, preferably aromatic polyfunctional isocyanates and also the modified polyfunctional isocyanates.
  • Suitable compounds having at least two isocyanate-reactive hydrogen atoms b) are generally those which carry at least two reactive groups selected from OH, SH, NH, NH 2 groups and CH-acidic groups in the molecule, in particular polyetherpolyols and / or the abovementioned polyester polyols having OH numbers in the range from 50 to 800 mg KOH / g.
  • the polyester polyols used usually have a functionality of 1.5-4 and an OH number of 50-400, preferably 150-300 mg KOH / g.
  • the polyether polyols are prepared by known processes, for example by anionic polymerization of alkylene oxides in the presence of catalysts, for example alkali metal hydroxides.
  • alkylene oxides used are usually ethylene oxide and / or propylene oxide, preferably pure 1,2-propylene oxide.
  • starting molecules having at least 2 to 8 hydroxyl groups in the molecule are preferably trimethylolpropane, glycerol, pentaerythritol, sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resoles, such as oligomeric condensation products of phenol and formaldehyde and Mannich condensates of phenols , Formaldehyde and dialkanolamines and melamine used.
  • starting molecules having at least two primary amino groups in the molecule are preferably aromatic di- and / or polyamines, for example phenylenediamines, 2,3-, 2,4-, 3,4- and 2,6-toluenediamine and 4,4'-, 2 , 4'- and 2,2'-diaminodiphenylmethane and aliphatic di- and polyamines, such as ethylenediamine used.
  • aromatic di- and / or polyamines for example phenylenediamines, 2,3-, 2,4-, 3,4- and 2,6-toluenediamine and 4,4'-, 2 , 4'- and 2,2'-diaminodiphenylmethane and aliphatic di- and polyamines, such as ethylenediamine used.
  • the polyether polyols have a functionality of preferably 2 to 8 and hydroxyl numbers of preferably 50 mg KOH / g to 800 mg KOH / g and in particular 150 mg KOH / g to 570 mg KOH / g.
  • the compounds having at least two isocyanate-reactive hydrogen atoms b) also include those optionally used with chain extenders and crosslinkers.
  • chain extenders and crosslinkers it is preferred to use alkanolamines, diols and / or triols, in particular diols and / or triols having molecular weights of less than 400, preferably 60 to 300.
  • Chain extenders, crosslinking agents or mixtures thereof are expediently used in an amount of 1 to 20% by weight, preferably 2 to 5% by weight, based on the polyol component b).
  • the rigid polyurethane foams are usually prepared in the presence of blowing agents, the abovementioned catalysts and cell stabilizers and, if necessary, further auxiliaries and / or additives which are generally known in polyurethane chemistry and in which DE-A-101 24 333 described, to which express reference is made.
  • auxiliaries and / or additives are the substances known per se for this purpose, for example surface-active substances, foam stabilizers, cell regulators, fillers, pigments, dyes, flameproofing agents, hydrolysis protection agents, antistatic agents, fungistatic and bacteriostatic agents.
  • the blowing agents used may be the chemical and / or physical blowing agents customary for polyurethane chemistry.
  • Chemical blowing agents are compounds which form gaseous products by reaction with isocyanate, such as, for example, water or formic acid.
  • Physical blowing agents are understood as compounds which are dissolved or emulsified in the starting materials of polyurethane production and evaporate under the conditions of polyurethane formation.
  • hydrocarbons such as pentane, cyclopentane, iso-pentane and mixtures of isomers, halogenated hydrocarbons, and other compounds such as perfluorinated alkanes such as perfluorohexane, chlorofluorocarbons, and ethers, esters, ketones and / or acetals.
  • the propellant component is usually used in an amount of 1 to 30 wt .-%, preferably 2 to 20 wt .-%, and particularly preferably 3 to 12 wt .-%, based on the total weight of the polyol component b), and depends according to the desired target density of rigid polyurethane foam.
  • flame retardants customary for polyurethane chemistry can be used.
  • catalysts and catalyst mixtures are used in addition, which catalyze the trimerization reaction of the NCO groups with each other.
  • examples include metal salts, especially ammonium, alkali or alkaline earth metal salts of carboxylic acids called.
  • the salts of linear or branched, substituted or unsubstituted, saturated or unsaturated carboxylic acids having 1 to 20 carbon atoms such as for example, formic acid, acetic acid, octanoic acid, tartaric acid, citric acid, oleic acid, stearic acid or ricinoleic acid or substituted or unsubstituted aromatic carboxylic acids having 6 to 20 carbons, such as benzoic acid or salicylic acid.
  • potassium formate potassium acetate
  • potassium octoate potassium 2-ethylhexanoate
  • ammonium formate ammonium acetate
  • ammonium octoate especially potassium formate and potassium acetate.
  • the rigid polyurethane foams can be prepared batchwise or continuously by means of known mixing devices.
  • the polyol component can be previously metered with separate pumps catalysts and / or propellant.
  • all reaction components are mixed simultaneously, usually in a mixing head.
  • the starting components are usually mixed at a temperature of 15 to 35 ° C, preferably from 20 to 30 ° C.
  • the components according to the invention preferably have a structure A-B-C-A 'or AB-C-B-A.
  • the microcapsules containing the latent heat storage material are contained in the polyurethane compact layer B according to the invention.
  • microcapsules are applied by means of the reactive polyurethane compact system on the metallic cover layer. This application can take place in an isolated process step or directly in the production of the sheet-like component.
  • microcapsules are dispersed in one or more of the starting components of the reactive polyurethane compact system.
  • the microcapsules can be suspended directly before mixing the starting components and the application to a cover layer or stored in stock suspended in one or more starting components.
  • the microcapsules are dispersed in the compound with at least two isocyanate-reactive hydrogen atoms b), preferably the polyol component.
  • the polyol component (without microcapsule additive) has a viscosity of 100-2000 mPa.s, preferably 150-800 mPa.s at 25 ° C.
  • a dispersant can be added to the polyol component as auxiliary agent.
  • Dispersants which may be mentioned are, for example, commercially available dispersants, such as the BYK-W additive series from BYK-Chemie GmbH. This allows the flow behavior of the storage material contained Component and the reactive polyurethane compact system can be improved and thus the processing can be facilitated.
  • the amount of microcapsules can be chosen freely and is determined by the desired amount of microcapsules per surface of the sheet-like component. In general, this is determined by the desired thickness of the reactive polyurethane compact system layer in the component and by the desired maximum processing viscosity of the starting components for the reactive polyurethane compact system.
  • 20 to 3000 g preferably 100 to 2000 g, in particular 500 to 1500 g of microcapsules per m 2 sheet-like component applied.
  • microcapsules based on the mixture of reactive polyurethane compact system and microcapsules are used.
  • the polyurethane compact layer generally has a thickness of 0.1 to 3 cm, preferably 0.25 to 2.5 cm, more preferably 0.5 to 2 cm, in particular 0.5 to 1.5 cm.
  • the device can be produced both batchwise and continuously.
  • the reaction mixture can also be poured into closed support tools (e.g., press molding) with high or low pressure metering machines.
  • closed support tools e.g., press molding
  • high or low pressure metering machines By means of this technology, for example, discontinuous composite elements according to the invention are produced.
  • the components are produced discontinuously, for example in a press mold.
  • the components are manufactured continuously, e.g. in a double belt plant.
  • the upper and lower metallic cover layers are then uncoiled from a roll and optionally profiled, heated and pretreated, e.g. Corona-treated to improve the foamability of the outer layers.
  • the different reaction mixtures each mixed, for example, in a high-pressure mixing head, successively applied to the lower cover layer and cured between the upper and lower cover layer in the so-called double band.
  • the endless strand is cut to the desired dimensions.
  • the present invention also relates to a process for the production of sheet-like structural elements comprising the application of a polyurethane compact layer (B) and a rigid polyurethane foam layer (C) to a metallic cover layer and Finally, the application of a second metal topcoat and optionally an additional polyurethane compact layer between the adjacent layers (A) and (C).
  • adhesion promoter it is possible to use a conventional adhesion promoter to achieve better adhesion between the layers (A) and (C), ie in the case of the layer structure (A) - (B) - (C) - (A).
  • adhesion promoters correspond chemically to the polyurethane compact system, with the difference that they contain no microcapsules.
  • the microcapsule-containing reactive polyurethane compact system is applied to a lower metallic cover layer, cures there, then follows the order of the reactive polyurethane foam system, which then foams and cures, optionally applied another layer of the microcapsule-containing reactive polyurethane compact system and finally the upper Applied metal topcoat.
  • the reactive polyurethane rigid foam system is applied to the metallic cover layer, foams there and cures, then follows the order of the reactive polyurethane compact system containing the microcapsules, and finally the upper cover layer is applied.
  • the time interval between application of the reactive foam system to the polyurethane compact system and the application of the reactive polyurethane compact system on the rigid foam system is chosen so that the polyurethane compact system or the rigid foam system is not fully cured to the adhesion between the two Improve systems.
  • the components according to the invention can also be produced with different metallic cover layer. They then have one or two thermally storable, near-surface layers directly behind the metal cover layer (s).
  • the thickness of the components of the invention is usually between 20 and 300 mm, the usual density range of rigid polyurethane foam for producing these moldings is 20 to 150 kg / m 3 , preferably 25 to 100 kg / m 3 (Kunststoffhandbuch, 3rd edition, page 150th ).
  • the components according to the invention enable the avoidance of barrack climate.
  • the buildings manufactured with them show not only good thermal insulation, but also a significant improvement in the temperature profile and thus in energy consumption.
  • the components are preferably used in residential construction, industrial construction, cold store construction, in sectional doors, in office containers or in caravan construction.
  • the sheet-like component made of composite material was produced with the aid of a cubic, tempered to 45 ° C and sealable form with the internal dimensions 20 x 20 x 8 cm (W x L x H).
  • a 20 x 20 cm sheet was placed on the bottom of the mold.
  • the lockable lid of the mold was slightly magnetic, so that another metal, 20 x 20 cm large sheet metal could be locked there.
  • the sidewalls of the mold were treated with a silicone-containing release agent to facilitate demoulding of the component later.
  • microcapsules prepared according to Example 1 of the WO 2008/006762 with a wall polymer of 20 parts by weight of methacrylic acid, 40 parts by weight of methyl methacrylate and 40 parts by weight of butanediol but with hexadecane as latent heat storage material
  • 60 g of the polyol component of the compact system 40 wt .-% dispersion.
  • the dispersion was then mixed with 50 g of Lupranat M 50 (polymeric MDI (NCO content 31.5% by weight) from BASF SE).
  • This mixture was applied as a 1 cm thick layer to a 20 x 20 cm sheet in the mold. After 2 minutes, a mixture of 85 g of polyol component of the rigid foam system and 85 g of Lupranat M 50 was applied to the ausreagierendes, containing microcapsules compact system and then closed the mold. After 8 minutes, the mold was reopened and a device obtained from bottom to top: a lower metallic cover layer, a polyurethane compact layer containing microcapsules, a rigid polyurethane foam layer and an upper metallic cover layer.
  • the two components showed the same thermal conductivity, however, a significantly higher amount of heat was absorbed in the device according to the invention until a constant heat flow.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Architecture (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Civil Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Building Environments (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Claims (10)

  1. Élément de construction de forme plate en un matériau composite, comprenant deux couches supérieures métalliques, une couche de mousse dure de polyuréthane et une couche compacte de polyuréthane, qui contient des microcapsules ayant un noyau de capsule en un matériau accumulateur de chaleur latent, la paroi de capsule des microcapsules étant constituée par
    30 à 100 % en poids d'un ou de plusieurs monomères (monomères I) du groupe comprenant les esters alkyliques en C1-C24 de l'acide acrylique et/ou méthacrylique, l'acide acrylique, l'acide méthacrylique et l'acide maléique,
    0 à 70 % en poids d'un ou de plusieurs monomères bi- ou polyfonctionnels (monomères II), qui ne sont pas solubles ou difficilement solubles dans l'eau, et
    0 à 40 % en poids d'un ou de plusieurs autres monomères (monomères III),
    à chaque fois par rapport au poids total des monomères.
  2. Élément de construction de forme plate selon la revendication 1, caractérisé en ce que l'élément présente la succession de couches suivante :
    1. une couche supérieure métallique (A),
    2. une couche compacte de polyuréthane (B),
    3. une couche de mousse dure de polyuréthane (C), et
    4. une couche supérieure métallique (A').
  3. Élément de construction de forme plate selon la revendication 1 ou 2, caractérisé en ce que la couche compacte de polyuréthane a une densité de 400 à 1 200 kg/m3.
  4. Élément de construction de forme plate selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la couche compacte de polyuréthane est formée par des di- et/ou polyisocyanates organiques, des polyéther-polyols et/ou des polyester-polyols, ainsi qu'un ou plusieurs catalyseurs et éventuellement des adjuvants.
  5. Élément de construction de forme plate selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le matériau accumulateur de chaleur latent est une substance lipophile organique ayant une transition de phase solide/liquide dans la plage de température allant de -20 à 120 °C.
  6. Élément de construction de forme plate selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la couche de mousse dure de polyuréthane a une densité moyenne de 20 à 150 kg/m3.
  7. Élément de construction de forme plate selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la couche de mousse dure de polyuréthane est formée par des di- et/ou polyisocyanates organiques, des polyéther-polyols et/ou des polyester-polyols, un agent gonflant et un ou plusieurs catalyseurs, ainsi qu'éventuellement d'autres adjuvants.
  8. Procédé de fabrication d'un élément de construction de forme plate selon l'une quelconque des revendications 1 à 7, comprenant l'application d'une couche compacte de polyuréthane (B) et d'une couche de mousse dure de polyuréthane (C) sur une couche supérieure métallique, puis l'application d'une deuxième couche supérieure métallique et éventuellement d'une couche compacte de polyuréthane supplémentaire entre les couches (A) et (C) voisines.
  9. Procédé de fabrication d'un élément de construction de forme plate selon la revendication 8, selon lequel il est fabriqué par un procédé continu.
  10. Utilisation de l'élément de construction de forme plate selon les revendications 1 à 7 dans la construction d'habitations, dans la construction de bâtiments industriels, dans la construction d'entrepôts frigorifiques, dans des portes sectionnables, dans des bureaux préfabriqués ou dans la construction de caravanes.
EP09763973.6A 2008-12-17 2009-12-04 Élément de construction de forme plate fait d'un matériau composite Active EP2379327B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL09763973T PL2379327T3 (pl) 2008-12-17 2009-12-04 Płaski element konstrukcyjny z materiału warstwowego
EP09763973.6A EP2379327B1 (fr) 2008-12-17 2009-12-04 Élément de construction de forme plate fait d'un matériau composite

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08171938 2008-12-17
EP09763973.6A EP2379327B1 (fr) 2008-12-17 2009-12-04 Élément de construction de forme plate fait d'un matériau composite
PCT/EP2009/066386 WO2010076118A1 (fr) 2008-12-17 2009-12-04 Élément de construction de forme plate fait d'un matériau composite

Publications (2)

Publication Number Publication Date
EP2379327A1 EP2379327A1 (fr) 2011-10-26
EP2379327B1 true EP2379327B1 (fr) 2017-11-08

Family

ID=41596123

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09763973.6A Active EP2379327B1 (fr) 2008-12-17 2009-12-04 Élément de construction de forme plate fait d'un matériau composite

Country Status (13)

Country Link
US (1) US8491992B2 (fr)
EP (1) EP2379327B1 (fr)
JP (1) JP5656864B2 (fr)
CN (1) CN102317073B (fr)
AR (1) AR074761A1 (fr)
BR (1) BRPI0922910A2 (fr)
CA (1) CA2746133A1 (fr)
ES (1) ES2657431T3 (fr)
MX (1) MX2011005878A (fr)
PL (1) PL2379327T3 (fr)
RU (1) RU2531347C2 (fr)
WO (1) WO2010076118A1 (fr)
ZA (1) ZA201105203B (fr)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011079299A1 (de) 2010-07-20 2012-01-26 Basf Se Verbundmaterials enthaltend Latentwärmespeicher
AU2012362118B2 (en) 2011-12-29 2016-11-17 Firestone Building Products Co., LLC Roofing membranes with expandable graphite as flame retardant
EP2800780B1 (fr) * 2012-01-03 2018-03-14 Phase Change Energy Solutions, Inc. Compositions comprenant des matériaux à changement de phase et leurs procédés de fabrication
EP2644374A1 (fr) * 2012-03-26 2013-10-02 Huntsman International LLC Panneau d'isolation
US9441140B2 (en) 2012-07-12 2016-09-13 Firestone Building Products Co., LLC Asphaltic sheet materials including expandable graphite
EP2703153A1 (fr) 2012-08-27 2014-03-05 Bayer MaterialScience AG Élément composite en sandwich avec des propriétés mécaniques améliorées et procédé de fabrication
WO2014048785A1 (fr) * 2012-09-28 2014-04-03 Basf Se Procédé de fabrication de profilés composites
DE102012218378A1 (de) * 2012-10-09 2014-04-10 Wacker Chemie Ag Flächengebilde oder Formkörper enthaltend latente Wärmespeicher
US10100513B2 (en) * 2012-11-05 2018-10-16 Basf Se Process for producing profiled elements
US8968853B2 (en) 2012-11-07 2015-03-03 Firestone Building Products Company, Llc Pressure-sensitive adhesives including expandable graphite
FR3001182B1 (fr) * 2013-01-18 2015-10-02 Bruno Prata Procede de plaquage metallique et element recouvert d'un plaquage metallique
US10017943B1 (en) 2013-02-14 2018-07-10 Firestone Building Products Co., LLC Liquid coatings including expandable graphite
JP6379357B2 (ja) * 2013-03-25 2018-08-29 パナソニックＩｐマネジメント株式会社 断熱シートおよびこれを用いた冷却構造
US10415249B2 (en) 2014-07-03 2019-09-17 Firestone Building Products Co., LLC EPDM roofing membranes with expandable graphite as flame retardant
EP3175053A1 (fr) * 2014-07-31 2017-06-07 Basf Se Système composite thermique à base de mousse de polyuréthane pour façades d'immeuble
FR3026046B1 (fr) * 2014-09-18 2019-10-04 Mci Technologies Ecran sous-toiture
US10624860B2 (en) 2017-03-21 2020-04-21 International Business Machines Corporation Method to generate microcapsules with hexahydrotriazine (HT)-containing shells
KR102105932B1 (ko) * 2018-11-22 2020-05-28 (주)비에이에너지 차열, 단열 및 방열기능을 동시에 갖는 전자 장비 수용 함체의 외벽 구조
CN110847415A (zh) * 2019-11-01 2020-02-28 东南大学 一种可全年发挥节能作用的建筑围护墙体

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2800457A (en) 1953-06-30 1957-07-23 Ncr Co Oil-containing microscopic capsules and method of making them
NL246986A (fr) 1959-01-02 1900-01-01
US3886085A (en) 1971-08-31 1975-05-27 Fuji Photo Film Co Ltd Process for producing fine oil-containing microcapsules having strong protective shells and microcapsules produced thereby
CA2012585A1 (fr) 1989-04-14 1990-10-14 The Mead Corporation Fabrication de composes d'impression a grande concentration en solides par microencapsulation en utilisant le vehicule d'impression en phase continue
RU2008776C1 (ru) * 1990-08-27 1994-03-15 Институт катализа СО РАН Теплоаккумулирующий материал
JP2684473B2 (ja) 1991-09-02 1997-12-03 富士写真フイルム株式会社 マイクロカプセルの連続的製造方法
JP3751028B2 (ja) 1992-02-28 2006-03-01 三菱製紙株式会社 蓄熱材用マイクロカプセル
DE4209632A1 (de) 1992-03-25 1993-09-30 Basf Ag Sulfogruppenhaltige Polymere
JPH1134222A (ja) * 1997-07-14 1999-02-09 Kansai Paint Co Ltd サンドイッチ構造パネル及びその製造方法
DE19749731A1 (de) 1997-11-11 1999-05-12 Basf Ag Verwendung von Mikrokapseln als Latentwärmespeicher
US6000438A (en) * 1998-02-13 1999-12-14 Mcdermott Technology, Inc. Phase change insulation for subsea flowlines
DE19833347A1 (de) 1998-07-24 2000-01-27 Basf Ag Formaldehydarme Dispersion von Mikrokapseln aus Melamin-Formaldehyd-Harzen
US6841209B2 (en) * 2000-01-12 2005-01-11 Fireking International, Inc. Fire protection containers incorporating novel low free-water insulation materials
DE10041162A1 (de) * 2000-08-21 2002-03-07 Basf Ag Verbundelemente enthaltend Polyisocyanat-Polyadditionsprodukte
DE10124333A1 (de) 2001-05-18 2002-11-21 Basf Ag Flammgeschützte PUR-Hartschaumstoffe mit reduziertem Flammschutzmittelanteil
DE10139171A1 (de) 2001-08-16 2003-02-27 Basf Ag Verwendung von Mikrokapseln in Gipskartonplatten
DE10163162A1 (de) 2001-12-20 2003-07-03 Basf Ag Mikrokapseln
US20050055982A1 (en) * 2003-08-13 2005-03-17 Medina Mario A. Phase-change structural insulated panels and walls
JP2005193612A (ja) * 2004-01-09 2005-07-21 Sanyo Chem Ind Ltd 硬質ポリウレタンフォーム
DE102004041298A1 (de) 2004-08-25 2006-03-02 Basf Ag Verbundelemente aus Polyurethan-Hartschaumstoff
EP1703033A3 (fr) 2005-02-23 2007-02-14 Corus Bausysteme GmbH Panneau intérieur de construction avec matériau à changement de phase
EP2043773B1 (fr) 2006-07-13 2009-12-16 Basf Se Microcapsules modifiées par polyélectrolytes
CN101528339B (zh) 2006-10-17 2013-03-27 巴斯夫欧洲公司 微胶囊
CN101547736B (zh) 2006-12-13 2013-11-13 巴斯夫欧洲公司 微胶囊

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
PL2379327T3 (pl) 2018-04-30
ES2657431T3 (es) 2018-03-05
ZA201105203B (en) 2012-09-26
US8491992B2 (en) 2013-07-23
CN102317073A (zh) 2012-01-11
US20110247215A1 (en) 2011-10-13
MX2011005878A (es) 2011-06-27
CA2746133A1 (fr) 2010-07-08
CN102317073B (zh) 2014-07-16
JP2012512063A (ja) 2012-05-31
EP2379327A1 (fr) 2011-10-26
BRPI0922910A2 (pt) 2016-01-26
RU2011129399A (ru) 2013-01-27
WO2010076118A1 (fr) 2010-07-08
JP5656864B2 (ja) 2015-01-21
AR074761A1 (es) 2011-02-09
RU2531347C2 (ru) 2014-10-20

Similar Documents

Publication Publication Date Title
EP2379327B1 (fr) Élément de construction de forme plate fait d'un matériau composite
EP1799736B2 (fr) Procede de production de mousses de polyurethanne rigides
EP1784546B1 (fr) Elements composites en mousse de polyurethane rigide
EP2134762B1 (fr) Tubes isolés
EP1753800B1 (fr) Polyurethanes syntactiques et leur utilisation pour isoler des installations en mer
EP2870188A2 (fr) Préparation de matériaux expansés à propriétés améliorées
WO2017207536A1 (fr) Procédé pour la préparation d'éléments de construction en sandwich
EP1571167B1 (fr) Procédé pour la préparation de mousses rigides à partir d'isocyanate
DE102005053101A1 (de) Gedämmte Rohre
DE4333795C2 (de) Verfahren zur Herstellung von thermoplastisch verformbaren Polyurethan-Hartschaumstoffen und hierfür verwendbare Mischungen aus Polyhydroxylverbindungen
DE2359610A1 (de) Organisch-anorganische kunststoffe und ein verfahren zu ihrer herstellung
DE102011079299A1 (de) Verbundmaterials enthaltend Latentwärmespeicher
DE102004049341A1 (de) Polyurethanhartschaumstoffe enthaltend Latentwärmespeicher
EP2900445B1 (fr) Procédé de fabrication de profilés composites
EP0934971B1 (fr) Procédé de préparation de mousses rigides de PU à faible diamètre de cellules, et leur utilisation
EP2641026A2 (fr) Procédé de fabrication d'éléments composites servant de panneaux rayonnants de plafond
WO2018138048A1 (fr) Formulation de polyuréthane souple à froid
DE2366240C3 (de) Organisch-anorganische Verbundkunststoffe
DE102004050937A1 (de) Verfahren zur Herstellung von Polyurethanhartschaumstoffen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20110718

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20170529

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASF COATINGS GMBH

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 943752

Country of ref document: AT

Kind code of ref document: T

Effective date: 20171115

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: AKZO NOBEL COATINGS INTERNATIONAL B.V.

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502009014519

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: BE

Ref legal event code: PD

Owner name: AKZO NOBEL COATINGS INTERNATIONAL BV; NL

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), CESSION; FORMER OWNER NAME: BASF COATINGS GMBH

Effective date: 20180117

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2657431

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20180305

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180208

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180208

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180308

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20180400348

Country of ref document: GR

Effective date: 20180518

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502009014519

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171204

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

26N No opposition filed

Effective date: 20180809

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171204

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171231

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171231

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20091204

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171108

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20221122

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20231121

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20231123

Year of fee payment: 15

Ref country code: GB

Payment date: 20231121

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20231124

Year of fee payment: 15

Ref country code: SE

Payment date: 20231121

Year of fee payment: 15

Ref country code: FR

Payment date: 20231122

Year of fee payment: 15

Ref country code: FI

Payment date: 20231121

Year of fee payment: 15

Ref country code: DE

Payment date: 20231121

Year of fee payment: 15

Ref country code: AT

Payment date: 20231123

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20231128

Year of fee payment: 15

Ref country code: BE

Payment date: 20231121

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20240102

Year of fee payment: 15